Printing



Patented June 4, 1935 UNITED STATES 2,003,960 PATIENT OFFICE PRINTINGRonald Tonkin and James Stevenson Wilson, Earls Road, Grangemouth,Scotland, assignors to Imperial Chemical Industries Limited,v acorporation, of Great Britain.

No Drawing. Application June 8, 1932, Serial No. 616,098. In GreatBritain June 16, 1931 20 Claims.

. reducing agents and assistants, and then aged bypassing through asteaming chamber, improper and uneven fixation of the color present inthe printing paste is liable to be encountered.

It is an object of the present invention to avoid or reduce theforegoing disadvantages. Further objects are the provision of newprinting assistants, new printing'pastes, and a new and improved'processof printing. A still further object is the production and use of highlyefficient vat color printing pastes. Other objects will appearhereinafter.

These objects are accomplished according to this invention byincorporating or including with printing pastes quaternary basecompounds of the following general formula:

Example I A printing paste is prepared according to the followingrecipe:

. Parts 3 3'-dichloro-dianthraquinone 1:2:2':1'-dihydroazine, singlestrength paste British gum thickening 9 Glycerine 2 Rongalite C- t g 1.8Potash 3.2 Choline chloride 4 Cotton cloth is printed with the foregoingpaste in the usual way, that is, by passing the cloth to be printedunder some tension and pressure over an intaglio metal roll, theengraving of which is filled withthe printing paste.

After leaving the printing machine the printed cloth is passed into adrier whereby the printing paste is dried on the cloth in its properplace and the dye is prevented from spreading to other portions of thefabric. In order" to complete the printing, the cloth, after leaving thedrier, is

passed into a steam ager for a period of a few minutes during which timethe vat color undergoes reduction and passes to the fiber. The fabric isthen subjected to oxidizing conditions which may include passing it intoa steeping bath, usually of water or water containing an oxidizingagent. Any excess color is washed off in a soap solution with which thetextile material is treated following the steeping. The printed materialpossesses stronger and brighter shades than are obtained withoutcholine-chloride.

Example II Instead of the dye3:3-dichloro-dianthraquinone-1:2:2':1'-dihydr0azine, Caledonv brown RS(4:5' di(benzoy1amino) 1:1'-dianthraquinonyl carbazole) paste is used inthe printing paste of Example I with good results.

Example III A printing paste is prepared according to thefollowingrecipe:

Parts 3 3'-dichloro-dianthraquinone 1:2:2' 1'-dihydroazine, .singlestrength paste 5 British gum thickening 11 Glycer I 2 Rongalite C 1.8Potash 3.2 .Cho1inechloride I- 2 Cotton cloth is printed with thispaste, dried, and steamed in the ager. The printed material possessesstronger and brighter shades than are obtained without choline chloride.

Example I? The 3:3dichloro-diahthraxiuinone-1:2:2' 1'- dihydroazine ofExamples I and III is replaced by 4 4 -dimethyl-6 :6 dichlorthioindigdpaste with very desirable results.

The new printing assistants preferably employed in accordance with theinvention are due.- ternary base compounds as already defined which arenon-volatile or substantially non-volatile under the conditionsof'operation and which are strong bases or salts of strong bases andwhich are hygroscopic or deliquescent. The results obtained with.-choline chloride in particular have been very highly advantageous. Thiscompound may be represented by the following formula;

CH3 CHaCHrOH CHa-N CH; Cl

- As further examples of the new printing assist- H: CH!

Hydroxyethyl trimethyl ammonium suifite o'momon cm omomon CHaN--O-SONCH:

g (EH:

13H: CH: 7 Hydroxyethyl trimethyl ammonium sulfate HO.CH2.0H: CHIC6HBCHa-N-C'l H: Benzyldimethyl hydroxyethyi ammonium chloride CHaCeHtHO.OH:.OH2-N-OH C s CH3 Benzyldimethyi hydroxyethyl ammonium hydroxideHO.CH:.CH1 CHzCtHs HO.CHa.OHi- H0.0Hz.CH: Cl

Benzyltrihydroxyethyl ammonium chloride H0.0H:.0H: OHZOIHI HO.GH:.OH:NOH

0113 Benzyl di(hydroxyethyl)methyl ammonium hydroxide HO-OHl-CH] CH;CH3- 0H,. 0.80;.Na Hydroxyethyl trimethyl ammonium sodium sulfateHO.CH:.CH| CH3 CHa-N ona o.so,.o,m Hydroxyethyl trimethyl ammoniumbenzenesulfonate H0.CH:.OH9 0H1 CHQ;N\ CH; 0.80:.H Hydroxyethyltrimethyl ammonium acid-sulfate It will be obseryed that the compoundsfalling within the invention may be classified in various ways. Thus,those of Formulae (4), .(9) and (11) are members of a group representedby the gen:

eral formula in which X is SO4 R (where R is hydrogen, metal, or anorganic radical, including the radical Ilia as already defined)Quarternary base compounds containing other stable acid residues suchas, for example, phosphates may be classified similarly. I

In practicing the invention, especially desirable results have beenobtained in printing vatcolors of the indanthrone series, particularly3:3'-dichloro dianthraquinone-l :2: 1' :2'-dihydroazine.

As examples of other printing colors may be mentioned: Caledon blue RC,6:6 diethoxy thioindigo, 7:7, dimethyl 5:5 dichlorthioindigo, 5:6:5':6'tetrabromindigo, bisbeta naphthionaphthene indigo and 4:4 dichlor- 5:5'dibromindigo.

As is well known a composition of printing paste may vary widely withdifferent dyes and manufacturers but, in the case of vat colors,

usually consists of a mixture 01 an unreduced vat dye, a strong reducingagent such as, sodium hydrosulphite or Rongalite, an alkali and athickening agent. The thickening agent is usually a gum (for instanceBritish gum), starch or both. Printing paste is usually preparedbymixing a dye paste or pastes with'the other ingredients enumerated,said other ingredients being in the form of a gummy mixture generallycalled a printing gum. The dye pastes are essentially finely dividedsuspensions of the dye with or without a dispersing agent. Printingassistants may be added to the dye paste or to the printing gum or theprinting paste as desired.

The amount of printing assistant may vary within relatively wide limitsbut may ordinarily be varied directly with the amount of dye. Empiricaltests can usually be made to determine the optimum amount of printingassistant for any given dye. Very satisfactory results are obtained-withproportions of printing assistant described in the examples but greateror lesser amounts may be employed if desired.

The process of the invention gives particularly valuable results withregard to fullness and brightness of shade when the sub-stratum uponwhich the color is printed is mercerized cotton. Good results are alsoobtained in printing other cotton materials and, in general, materialswhich may be printed with vat colors including viscose rayon and othrfibers, fabrics and yarns of vegetable origin.

While the invention is not limited to any theory, inasmuch as thequarternary bases employed as printing assistants are, in general, verydeliquescent substances it appears probable that this property ofdeliquesence ispartly or wholly responsible for the improved resultswhich are obtained by their use. .It may be that their presence assistsin the absorption 01 water either before or during the steamingoperation, by which means the conditions requisite for the properfixation of the color are attained. They may also,

in some cases, exert a solvent action on the color. Most deliquescentinorganic salts are incompatible'with the alkaline mixtures used inprinting, especially with vat colors, being decomposed to givedifiicultly soluble hydroxides, oxides or ants is such that by their usegreatly improved prints may be obtained with dyes which are ordinarilypoor printing colors such as, for example, 3 3-dichloro-dianthraquinone1:2:2' :1-dihydroazine.

As many apparent'and widely different embodiments of this invention maybe made without departing from the spirit thereof, it is to beunderstood that we do not limit ourselves to the foregoing examples ordescription except as indicated in the following claims.

We claim:

1. Vat dye pastes comprising a water-insoluble vat dye and a quaternarybase compound of the general formula where R1, Ra, R: and R4 are thesame or different alkyl or aralkyl groups, one at least of which is analkyl group containing a hydroxy group, and where X represents OH or anacid residue.

2. Vat dye textile printing pastes comprising a water-insoluble vat dyeand choline or a salt thereof. r

"-3. Vat dy e printing pastes comprising a waterinsoluble vat dye and awater-soluble quaternary base compound of the general formula where R1,Ra, R3 and R4 are the same or different alkyl groups, one at least ofwhich contains a hydroxy group, and where X represents OH or an acidresidue.

4. Vat dye printing pastes comprising a waterinsoluble vat dye and awater-soluble quaternary base compound of the general formula Ill:X-N-Rz where R1, Ra, R: and R4 are the same or diiferen alkyl or aralkylgroups, one at least of which is an alkyl group containing a hydroxygroup, and where X represents an inorganic acid residue.

5. A vat dye paste comprising a water-insoluble vat. dye and cholinechloride.

'6. Printing pastes comprising. an anthraquinone vat dye and awater-soluble quaternary base compound of the general formula I'M 1X-N-lt:

where R1, Ra, R: and Rare the same or different alkyl or aralkyl groups,one at least of which is an alkyl group containing a hydroxy group andwhere X represents -OH or an 'acid residue.

- '1. A process of printing textiles comprising adding to a pastecontaining a vat dye and other customary ingredients a water-solublequaternary base compound of the general formula B" X--I|-I'R:

. where R1, R2, R2, and Ra are the same or different alkyl or aralkylgroups, one at least of which is an" alkyl group containing where xrepresents --OH or an acid residue and a hydroxy group and thereafterusing the compounded paste in prlntclaim 7 wherein the paste contains avat dye and choline or a salt thereof. r

9. A process of printing textiles as claimed in claim '7 wherein thedyestuif is 3'z3'z-dichlorodianthraquinone-1:2:2':1'-dihydroazine.

".10. A process of printing textiles as claimed in claim 7 wherein thedye is a chloro dianthraquinone-1:2:2':1'-dihydroazine.

11. A process of printing textiles as claimed in claim? wherein thepastecontains a chloro d1- anthroquinone-l :2 :2 :1--dihydroazine and cholinechloride.

12. A dye paste of a. halogenated dianthraquinone-1:2:2':1'-dihydroazine containing as an ingredient choline chloride.

13. A dye paste of a chloro dianthraquinonel:2:2:1'-dihydroazinecontaining as an ingredi ent choline chloride.

14. A dye paste of 3:3-dichloro-dianthraquinone-1:2:2:1-dihydroazinecontaining as an ingredient choline chloride.

15. A thioindigoid dye paste containing as an ingredient cholinechloride.

16. A dye paste of 4:4'-dimethyl-6:6- -dichlorthioindigo containing asan ingredient choline chloride.

1'7. A dye paste of a di(benzoylamino) -l:1'-dianthraquinonyl carbazolecontaining as an ingredient choline chloride.

18. A dye paste comprising a water insoluble vat dye and a water-solublequaternary base compound of the general formula:

where R1, Ra, R: and R4 are the same or different alkyl or aralkylgroups, one at least of which is an alkyl group'containing a hydroxygroup, and where X represents OH or an acid residue.

20. The process of printing vat dyes which I comprises applying to thefiber a printing paste comprising the vat dye, an alkali, a reducingagent suitable for printing, a gum thickening agent, and a quaternarybase compound of the general formula:

t R: t wherein R1, Ra, R: and R4 are the same or diflerent alkyl oraralkyl groups, one at least of which is an alkyl group containing ahydroxy rou and wherex represents OH or an acid residue, and thereafterdeveloping the print.

RONALD 'I'ONKIN.

JAMES STEVENSON wit-son. v i

